WO2022181692A1 - カーボンナノチューブ集合線の製造方法及びカーボンナノチューブ集合線製造装置 - Google Patents

カーボンナノチューブ集合線の製造方法及びカーボンナノチューブ集合線製造装置 Download PDF

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WO2022181692A1
WO2022181692A1 PCT/JP2022/007606 JP2022007606W WO2022181692A1 WO 2022181692 A1 WO2022181692 A1 WO 2022181692A1 JP 2022007606 W JP2022007606 W JP 2022007606W WO 2022181692 A1 WO2022181692 A1 WO 2022181692A1
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carbon nanotube
carbon
channel
flow path
cnt
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PCT/JP2022/007606
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English (en)
French (fr)
Japanese (ja)
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威 日方
利彦 藤森
大之 山下
総一郎 大久保
伯薫 小野木
淳一 藤田
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住友電気工業株式会社
国立大学法人 筑波大学
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Priority to JP2023502487A priority Critical patent/JPWO2022181692A1/ja
Priority to CN202280015527.4A priority patent/CN116888068A/zh
Priority to US18/277,855 priority patent/US20240308853A1/en
Publication of WO2022181692A1 publication Critical patent/WO2022181692A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/164—Preparation involving continuous processes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D01F9/133—Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/34—Length
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

Definitions

  • the present disclosure relates to a carbon nanotube stranded wire manufacturing method and a carbon nanotube stranded wire manufacturing apparatus.
  • Carbon nanotubes (hereinafter also referred to as "CNTs”), which have a cylindrical structure of graphene sheets in which carbon atoms are hexagonally bonded, are 1/5 lighter than copper, 20 times stronger than steel, and have excellent conductivity. It is a material with properties. Therefore, electric wires using carbon nanotubes are expected as a material that contributes to weight reduction, downsizing, and improvement of corrosion resistance of motors for automobiles.
  • Carbon nanotubes currently produced have a diameter of about 0.4 nm to 20 nm and a maximum length of about 55 cm.
  • it is necessary to make the wire rod longer, and techniques for obtaining an elongated wire rod using the carbon nanotube are being studied.
  • Patent Document 1 discloses a method of obtaining an elongated carbon nanotube assembly line by aligning and assembling a plurality of carbon nanotubes in their longitudinal direction. It is
  • the method for producing the carbon nanotube stranded wire of the present disclosure includes: A first step of growing carbon nanotubes from each of the plurality of catalyst particles in a tubular carbon nanotube synthesis furnace to obtain a plurality of carbon nanotubes by supplying a carbon-containing gas to the plurality of catalyst particles in a floating state.
  • a second step of assembling the plurality of carbon nanotubes to obtain a plurality of assembled carbon nanotube wires is 2A obtaining a first carbon nanotube assembly line by aligning and assembling a first carbon nanotube group composed of a portion of the plurality of carbon nanotubes in a first channel along the longitudinal direction of the carbon nanotubes; process and a second carbon nanotube group composed of a part of the plurality of carbon nanotubes different from the plurality of carbon nanotubes constituting the first carbon nanotube group is oriented along the longitudinal direction of the carbon nanotubes in the second channel; and a second B step of obtaining a second woven carbon nanotube wire by assembling the carbon nanotube woven wires.
  • the carbon nanotube assembly wire manufacturing equipment is a tubular carbon nanotube synthesis furnace; a carbon-containing gas supply port provided at one end of the carbon nanotube synthesis furnace; a first flow path and a second flow path provided on the opposite end side of the carbon nanotube synthesis furnace from the end where the carbon-containing gas supply port is provided;
  • the first flow path and the second flow path are provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace,
  • the cross-sectional area of each of the first channel and the second channel is smaller than the cross-sectional area of the carbon nanotube synthesis furnace.
  • FIG. 1 is a flow chart showing a method for manufacturing a carbon nanotube stranded wire according to Embodiment 1.
  • FIG. FIG. 2 is a diagram showing an example of a carbon nanotube stranded wire manufacturing apparatus according to Embodiment 2.
  • FIG. 3 is a flow chart showing a method for manufacturing a carbon nanotube stranded wire according to the third embodiment.
  • FIG. 4 is a diagram showing an example of a carbon nanotube stranded wire manufacturing apparatus according to a fourth embodiment.
  • FIG. 7 is a diagram showing an example of a carbon nanotube stranded line manufacturing apparatus according to Embodiment 5.
  • FIG. FIG. 8 is a diagram showing an example of the main surface of the 1-3 structure on the carbon-containing gas supply port side.
  • FIG. 9 is a diagram showing an example of the main surface on the side opposite to the main surface on the carbon-containing gas supply port side of the 1-3 structure.
  • FIG. 10 is a diagram showing an example of a cross section of the 1-3 structure.
  • FIG. 11 is a diagram showing an apparatus 4 (carbon nanotube stranded wire manufacturing apparatus of a comparative example).
  • FIG. 12 is a diagram showing a cross section of the 1-1 structure of the device 5 (comparative carbon nanotube stranded wire manufacturing device).
  • one carbon nanotube assembly line can be obtained from one carbon nanotube synthesis furnace.
  • a technique for producing a plurality of stranded carbon nanotube wires from one carbon nanotube synthesis furnace is desired.
  • one of the objects of the present invention is to provide a method for producing a carbon nanotube stranded wire, which can produce a plurality of carbon nanotube stranded wires with one carbon nanotube synthesis furnace.
  • Another object of the present invention is to provide a carbon nanotube assembly wire manufacturing apparatus capable of manufacturing a plurality of carbon nanotube assembly wires with one carbon nanotube synthesis furnace.
  • the method for producing a carbon nanotube stranded wire of the present disclosure includes: A first step of growing carbon nanotubes from each of the plurality of catalyst particles in a tubular carbon nanotube synthesis furnace to obtain a plurality of carbon nanotubes by supplying a carbon-containing gas to the plurality of catalyst particles in a floating state.
  • a second step of assembling the plurality of carbon nanotubes to obtain a plurality of assembled carbon nanotube wires is 2A obtaining a first carbon nanotube assembly line by aligning and assembling a first carbon nanotube group composed of a portion of the plurality of carbon nanotubes in a first channel along the longitudinal direction of the carbon nanotubes; process and a second carbon nanotube group composed of a part of the plurality of carbon nanotubes different from the plurality of carbon nanotubes constituting the first carbon nanotube group is oriented along the longitudinal direction of the carbon nanotubes in the second channel; and a second B step of obtaining a second woven carbon nanotube wire by assembling the carbon nanotube woven wires.
  • the first carbon nanotube group includes a first A carbon nanotube group composed of a portion of a plurality of carbon nanotubes constituting the first carbon nanotube group, and a plurality of carbons constituting the first A carbon nanotube group. a first carbon nanotube group composed of a part of the plurality of carbon nanotubes constituting the first carbon nanotube group different from nanotubes,
  • the first flow path includes a 1-1A flow path and a 1-1a flow path provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace, and a 1-1A flow path and the 1-1A flow path.
  • the 2nd A step is a 2A-1A step of orienting and assembling the 1A carbon nanotube groups along the longitudinal direction of the carbon nanotubes in the 1-1A channel to obtain a 1A carbon nanotube aggregate strand; a 2A-1a step of orienting and assembling the 1a carbon nanotube groups along the longitudinal direction of the carbon nanotubes in the 1-1a channel to obtain a 1a carbon nanotube aggregated wire; A plurality of carbon nanotube-assembled strands including the firstA carbon nanotube-assembled strand and the firsta carbon nanotube-assembled strand are oriented along the longitudinal direction of the carbon nanotube-assembled strand within the first-second channel.
  • the second carbon nanotube group is composed of a second B carbon nanotube group composed of a part of a plurality of carbon nanotubes constituting the second carbon nanotube group, and a plurality of carbon nanotubes constituting the second B carbon nanotube group.
  • a 2b carbon nanotube group composed of a part of the plurality of carbon nanotubes constituting the different second carbon nanotube group
  • the second flow path includes the 2-1B flow path and the 2-1b flow path, which are provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace, and the 2-1B flow path and the 2-1B flow path.
  • the 2B step is a 2B-1B step of orienting and assembling the 2B carbon nanotube groups along the longitudinal direction of the carbon nanotubes in the 2-1B channel to obtain a 2B carbon nanotube assembly strand; a 2B-1b step of orienting and assembling the 2b carbon nanotube groups along the longitudinal direction of the carbon nanotubes in the 2b channel to obtain a 2b carbon nanotube aggregate strand; A plurality of carbon nanotube-assembled strands including the 2B carbon nanotube-assembled strand and the 2b carbon nanotube-assembled strand are oriented along the longitudinal direction of the carbon nanotube-assembled strand within the 2-2 channel. and a step 2B-2 of assembling the carbon nanotubes to obtain the second assemble line of carbon nanotubes.
  • carbon nanotubes are aggregated to form a carbon nanotube aggregated wire, and further, the carbon nanotube aggregated wire is aggregated to form a carbon nanotube aggregated wire.
  • the carbon nanotube aggregated wire tends to be elongated. It is preferable that the 2-1 flow path and the 2-2 flow path draw the CNT generated in the first flow path into each flow path by respectively sucking.
  • the carbon nanotube assembly wire manufacturing apparatus of the present disclosure is a tubular carbon nanotube synthesis furnace; a carbon-containing gas supply port provided at one end of the carbon nanotube synthesis furnace; a first flow path and a second flow path provided on the opposite end side of the carbon nanotube synthesis furnace from the end where the carbon-containing gas supply port is provided;
  • the first flow path and the second flow path are provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace,
  • the cross-sectional area of each of the first channel and the second channel is smaller than the cross-sectional area of the carbon nanotube synthesis furnace.
  • the first flow path includes a 1-1A flow path and a 1-1a flow path provided in parallel on the carbon-containing gas supply port side of the carbon nanotube synthesis furnace, and the 1-1A flow and a 1-2 channel provided on the opposite side of the carbon-containing gas supply port of the 1-1a channel
  • the second flow path includes the 2-1B flow path and the 2-1b flow path provided in parallel on the carbon-containing gas supply port side of the carbon nanotube synthesis furnace, and the 2-1B flow path and the and a 2-2 channel provided on the opposite side of the 2-1b channel to the carbon-containing gas supply port.
  • carbon nanotubes are aggregated to form a carbon nanotube aggregated wire, and further, the carbon nanotube aggregated wire is aggregated to form a carbon nanotube aggregated wire.
  • the carbon nanotube aggregated wire tends to be elongated.
  • the 1-1A channel, the 1-1a channel, the 2-1B channel and the 2-1b channel are provided in the same 1-1 structure
  • the 1-2 channel is provided in a 1-2 structure different from the 1-1 structure
  • the 2-2 channel is preferably provided in a 2-2 structure different from the 1-1 structure.
  • the carbon nanotubes and the carbon nanotube assembly lines are easily oriented and aggregated in the longitudinal direction.
  • the 1-1A channel, the 1-1a channel, the 1-2 channel, the 2-1B channel, the 2-1b channel and the 2-2 channel is provided in the same 1-3 structure,
  • the end of each of the 1-1A flow path and the 1-1a flow path opposite to the carbon-containing gas supply port is the end of the 1-2 flow path on the carbon-containing gas supply port side.
  • the end of each of the 2-1B flow path and the 2-1b flow path opposite to the carbon-containing gas supply port is the end of the 2-2 flow path on the carbon-containing gas supply port side. is preferably connected to
  • the carbon nanotubes and the carbon nanotube assembly lines are easily oriented and aggregated in the longitudinal direction.
  • FIG. 1 is a diagram showing a flow chart of a method for manufacturing a carbon nanotube-assembled wire (hereinafter also referred to as "CNT-assembled wire”) according to the present embodiment.
  • FIG. 2 is a diagram showing an example of a carbon nanotube stranded wire manufacturing apparatus used in the carbon nanotube stranded wire manufacturing method of the present embodiment.
  • a tubular carbon nanotube synthesis furnace (hereinafter also referred to as a “CNT synthesis furnace”) 60 contains a plurality of suspended carbon nanotube wires.
  • the plurality of carbon nanotubes constituting the first carbon nanotube group 11 are in a separated state before entering the first channel 41 without forming a network that hinders the separation. It is preferable that the plurality of carbon nanotubes constituting the second carbon nanotube group 12 are in a state of being separated from each other before entering the second channel 42 without forming a network that hinders the separation. According to this, it is possible to prevent clogging of the plurality of carbon nanotubes near the entrance of the first channel and near the entrance of the second channel.
  • a plurality of carbon nanotube assembly wires can be obtained with one carbon nanotube synthesis furnace. As a result, it becomes easier to increase the size of the CNT synthesis furnace and to mass-produce the CNT-assembled wire, thereby making it possible to reduce the manufacturing cost of the CNT-assembled wire.
  • the first step is preferably performed under temperature conditions of, for example, 800°C or higher and 1500°C or lower. Under temperature conditions of 800° C. or more and 1500° C. or less, the carbon-containing gas is thermally decomposed, and carbon crystals grow on the catalyst particles in a suspended state to form carbon nanotubes. It is also possible to grow CNTs between the plurality of catalyst particles by separating the plurality of catalyst particles in close contact with each other in the flow of the carbon-containing gas.
  • the temperature condition of the first step is more preferably 900° C. or higher and 1400° C. or lower, and still more preferably 950° C. or higher and 1250° C. or lower.
  • the catalyst particles 27 are suspended in the carbon-containing gas supplied to the CNT synthesis furnace 60.
  • the catalyst particles 27 are obtained by spraying a slurry in which a catalyst material is dissolved from a spray nozzle arranged near a carbon-containing gas supply port in the CNT synthesis furnace 60.
  • a catalyst (not shown) obtained by heating is heated, and carbon It collapses into particles due to the wind pressure of the contained gas.
  • catalyst materials include ferrocene (Fe(C 5 H 5 ) 2 ), nickelocene (Ni(C 5 H 5 ) 2 ), cobaltocene (Co(C 5 H 5 ) 2 etc.) and the like.
  • ferrocene is preferable from the viewpoint of being excellent in disintegration property and catalytic action and being able to obtain long CNTs.
  • ferrocene is heated to a high temperature and exposed to a carbon-containing gas, it carburizes to form iron carbide (Fe 3 C) on the surface, which easily collapses from the surface, thereby sequentially releasing the catalyst particles 27 . It is possible.
  • the main component of the formed catalyst particles 27 is iron carbide or iron.
  • catalyst particles 27 other than the above for example, nickel, cobalt, molybdenum, gold, silver, copper, palladium, and platinum can be used.
  • the lower limit of the average diameter of the catalyst particles 27 is preferably 0.4 nm or more, more preferably 1 nm or more, and even more preferably 2 nm or more.
  • the upper limit of the average diameter of the catalyst particles 27 is preferably 20 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less.
  • a carbon-containing gas is supplied to the CNT synthesis furnace 60 from a carbon-containing gas supply port 62 .
  • a reducing gas such as a hydrocarbon gas is used.
  • examples of such a carbon-containing gas include a mixed gas of methane and argon, a mixed gas of ethylene and argon, a mixed gas of ethanol and argon, a mixed gas of ethylene and hydrogen, a mixed gas of methane and hydrogen, ethanol and A mixed gas of hydrogen or the like can be used.
  • the carbon - containing gas contains carbon disulfide (CS2) as a co-catalyst.
  • the lower limit of the average flow velocity in the CNT synthesis furnace of the carbon-containing gas supplied from the carbon-containing gas supply port 62 is preferably 0.05 cm/sec or more, more preferably 0.10 cm/sec or more, and 0.20 cm/sec. The above is more preferable.
  • the upper limit of the average flow velocity in the CNT synthesis furnace 60 is preferably 50 cm/sec or less, more preferably 5.0 cm/sec or less.
  • the average flow velocity of the carbon-containing gas in the CNT synthesis furnace 60 is 0.05 cm/sec or more, the carbon-containing gas supplied to the catalyst particles 27 is sufficient, and the carbon nanotubes synthesized between the catalyst particles 27 grow. is promoted.
  • the average flow velocity of the carbon-containing gas in the CNT synthesis furnace 60 is 10.0 cm/sec or less, it is possible to suppress the separation of the carbon nanotubes from the catalyst particles 27 and stop the growth of the carbon nanotubes.
  • the lower limit of the Reynolds number of the flow in the CNT synthesis furnace 60 of the carbon-containing gas supplied from the carbon-containing gas supply port 62 is preferably 0.01 or more, more preferably 0.05 or more.
  • the upper limit of the Reynolds number is preferably 1000 or less, more preferably 100 or less, and even more preferably 10 or less.
  • the Reynolds number is 0.01 or more, the degree of freedom in device design is improved.
  • the Reynolds number is 1000 or less, it is possible to prevent the flow of the carbon-containing gas from being disturbed and the orientation of the carbon nanotubes between the catalyst particles 27 to be inhibited.
  • the carbon nanotubes 1 obtained in the first step include single-walled carbon nanotubes in which only one carbon layer (graphene) is cylindrical, and carbon nanotubes in which a plurality of carbon layers are stacked to form a cylindrical shape. Examples include double-walled carbon nanotubes, multi-walled carbon nanotubes, and the like.
  • the shape of the carbon nanotube is not particularly limited, and examples include those with closed ends and those with open holes at the ends.
  • catalyst particles 27 used during synthesis of the carbon nanotube may be attached to one or both ends of the carbon nanotube 1 .
  • one or both ends of the carbon nanotube 1 may be formed with a conical cone made of graphene.
  • the length of the carbon nanotube is, for example, preferably 1 ⁇ m or longer, more preferably 10 ⁇ m or longer.
  • carbon nanotubes with a length of 100 ⁇ m or more are preferable from the viewpoint of production of CNT-assembled wires.
  • the upper limit of the length of the carbon nanotube is not particularly limited, it is preferably 600 mm or less from the viewpoint of manufacturing.
  • the length of CNT can be measured by observing with a scanning electron microscope.
  • the diameter of the carbon nanotube is preferably 0.4 nm or more and 20 nm or less, more preferably 1 nm or more and 10 nm or less.
  • carbon nanotubes with a diameter of 1 nm or more and 10 nm or less are preferable from the viewpoint of high density and high adhesion.
  • the diameter of a carbon nanotube means the average outer diameter of one CNT.
  • the average outer diameter of the CNT is obtained by directly observing the cross section of the CNT at any two locations with a transmission electron microscope, and measuring the outer diameter, which is the distance between the two most distant points on the outer circumference of the CNT in the cross section, It is obtained by calculating the average value of the obtained outer diameters. If the CNT contains a cone on one or both ends, measure the diameter at the location excluding the cone.
  • a second step is performed in which a plurality of carbon nanotubes obtained in the first step are aggregated to obtain a plurality of carbon nanotube aggregated lines (hereinafter also referred to as "CNT aggregated lines").
  • the second step includes a 2A step and a 2B step. The 2A step and the 2B step are described below.
  • the first carbon nanotube group 11 composed of a part of the plurality of carbon nanotubes 1 obtained in the first step is oriented along the longitudinal direction of the carbon nanotubes in the first flow channel 41.
  • the carbon nanotubes are assembled to obtain the first carbon nanotube assembly line 31 .
  • a plurality of CNTs 1 synthesized in the CNT synthesis furnace 60 enter the first channel 41 with their longitudinal direction along the flow of the carbon-containing gas.
  • the first flow path 41 is arranged such that its longitudinal direction follows the flow of the carbon-containing gas.
  • the cross-sectional area normal to the flow of the carbon-containing gas in the first flow path 41 is smaller than the cross-sectional area normal to the flow of the carbon-containing gas in the CNT synthesis furnace 60 . Therefore, the plurality of CNTs 1 that have entered the first channel 41 are oriented and aggregated along the longitudinal direction of the CNTs in the first channel 41 to form the first CNT assembly line 31 .
  • the second carbon nanotubes 1 obtained in the first step which are different from the plurality of carbon nanotubes constituting the first carbon nanotube group 11, are composed of a portion of the second carbon nanotubes.
  • the nanotube groups 12 are oriented and aggregated along the longitudinal direction of the carbon nanotubes in the second channel 42 to obtain the second aggregated carbon nanotube line 32 .
  • a plurality of CNTs 1 synthesized in the CNT synthesis furnace 60 enter the second channel 42 with their longitudinal direction along the flow of the carbon-containing gas.
  • the second flow path 42 is arranged such that its longitudinal direction follows the flow of the carbon-containing gas.
  • the cross-sectional area normal to the flow of the carbon-containing gas in the second channel 42 is smaller than the cross-sectional area normal to the flow of the carbon-containing gas in the CNT synthesis furnace 60 . Therefore, the plurality of CNTs 1 that have entered the second channel 42 are oriented and aggregated along the longitudinal direction of the CNTs to form the second CNT assembly line 32 .
  • the method for producing a CNT-assembled wire In the method for producing a CNT-assembled wire according to the present embodiment, some of a plurality of CNTs synthesized in one CNT synthesis furnace are oriented and aggregated in the first channel to produce the first CNT-assembled wire 31, Another part of the plurality of CNTs is oriented and aggregated in the second channel to produce the second CNT-aggregated line 32 . That is, in the method for producing a CNT-assembled wire according to the present embodiment, two CNT-assembled wires can be produced using one CNT synthesis furnace.
  • the second step includes two steps, 2A step and 2B step, and shows the case of obtaining two CNT-assembled lines, but the form of the second step is limited to this. not.
  • the number of CNT-assembled lines obtained can be increased.
  • the number of channels matches the number of CNT-assembled lines obtained. Therefore, if the number of flow paths is three, three CNT assembly lines are obtained, and if the number of flow paths is four, four CNT assembly lines are obtained.
  • the number of carbon nanotubes constituting each of the first carbon nanotube group 11 and the second carbon nanotube group 12 is It is adjusted according to the line and diameter of the wire.
  • the shape of the carbon nanotube aggregated wire obtained by the second step is a thread shape in which a plurality of carbon nanotubes are aligned and aggregated in their longitudinal direction.
  • the length of the carbon nanotube aggregated wire is not particularly limited, and can be appropriately adjusted depending on the application.
  • the lower limit of the length of the CNT-assembled wire is, for example, preferably 100 ⁇ m or longer, more preferably 1000 ⁇ m or longer, and even more preferably 10 cm or longer.
  • the upper limit of the length of the CNT-assembled wire is not particularly limited, it can be 100 km or less from the viewpoint of manufacturing.
  • the length of the CNT aggregate line is preferably 100 ⁇ m or more and 100 km or less, more preferably 1000 ⁇ m or more and 10 km or less, and even more preferably 10 cm or more and 1 km or less.
  • the length of CNT-assembled lines is measured by scanning electron microscopy, optical microscopy, or visual observation.
  • the size of the diameter of the carbon nanotube aggregated wire is not particularly limited, and can be appropriately adjusted depending on the application.
  • the lower limit of the diameter of the CNT-assembled wire is, for example, preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably over 100 ⁇ m, and even more preferably 1000 ⁇ m or more.
  • the upper limit of the diameter of the CNT-assembled wire is not particularly limited, it can be set to 10000 ⁇ m or less from the viewpoint of manufacturing.
  • the diameter of the CNT-assembled wire is preferably 1 ⁇ m or more and 10000 ⁇ m or less, more preferably 10 ⁇ m or more and 1000 ⁇ m or less, still more preferably 100 ⁇ m or more and 1000 ⁇ m or less, and still more preferably 300 ⁇ m or more and 1000 ⁇ m or less.
  • the diameter of the CNT-assembled wire is smaller than the length of the CNT-assembled wire. That is, the longitudinal direction corresponds to the lengthwise direction of the CNT-aggregated wire.
  • the diameter of the carbon nanotube aggregated wire means the average outer diameter of one CNT aggregated wire.
  • the average outer diameter of one CNT-assembled wire is obtained by observing the cross section at any two points of one CNT-assembled wire with a transmission electron microscope, scanning electron microscope, or optical microscope, and It is obtained by measuring the outer diameter, which is the distance between the two most distant points, and calculating the average value of the obtained outer diameters.
  • TEM Transmission electron microscope
  • JEM2100 product name
  • Imaging conditions magnification of 50,000 to 1,200,000 times, acceleration voltage of 60 kV to 200 kV.
  • Image processing program Nondestructive paper surface fiber orientation analysis program "FiberOri8single03" (http://www.enomae.com/FiberOri/index.htm) Processing procedure: 1. Histogram average brightness correction 2 . 3. background subtraction; 4. Binarization with a single threshold; Brightness inversion.
  • Orientation (180°-full width at half maximum)/180° (1)
  • degree of orientation 0
  • a degree of orientation of 1 means complete orientation.
  • the degree of orientation is 0.8 or more and 1.0 or less, it is determined that a plurality of CNTs are aligned and aggregated in the longitudinal direction on the CNT assembly line.
  • the CNT assembly line is elongated while maintaining the electrical conductivity and mechanical strength characteristics of the CNTs. .
  • the method for manufacturing a CNT-assembled wire according to the present embodiment includes, after the second step, a third step of attaching a volatile liquid to a plurality of carbon nanotube-assembled wires, and evaporating the volatile liquid attached to the carbon nanotube-assembled wires. It is preferable to include a fourth step. According to this, the carbon nanotubes can be uniformly and densely adhered to each other in the process in which the liquid permeated between the carbon nanotubes volatilizes and escapes.
  • Volatile liquids include, for example, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, xylene, anisole, toluene, cresol, pyrrolidone, carbitol, carbitol acetate, water, epoxy monomers, acrylic monomers, chlorosulfonic acid, nitric acid, Sulfuric acid can be used. Volatile liquids may include monomers or resins or acids.
  • the third step can be performed by, for example, using the liquid adhesion device 63 to atomize the volatile liquid into vapor and spray the vapor onto the CNT aggregate wire.
  • the fourth step can be performed by natural drying.
  • the third and fourth steps are preferably carried out while applying tension to the CNT wire by winding the carbon nanotube wire with the winding device 64 . According to this, the strength of the obtained CNT-assembled wire is improved.
  • the carbon nanotube assembly wire manufacturing apparatus 100a of the present embodiment includes a tubular carbon nanotube synthesis furnace 60 and one end side (left side in FIG. 2) of the carbon nanotube synthesis furnace 60. a carbon-containing gas supply port 62, and a first flow provided on the end (right side in FIG. 2) opposite to the end of the carbon nanotube synthesis furnace 60 where the carbon-containing gas supply port 62 is provided.
  • a channel 41 and a second channel 42 are provided, the first channel 41 and the second channel 42 are provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace 60, and the first channel 41 and the second channel 42 have a smaller cross-sectional area than the carbon nanotube synthesis furnace 60 .
  • a carbon nanotube synthesis furnace (hereinafter also referred to as “CNT synthesis furnace”) 60 has a tubular shape made of, for example, a quartz tube. Carbon nanotubes 1 are formed on catalyst particles 27 in a CNT synthesis furnace 60 using a carbon-containing gas.
  • the carbon nanotube synthesis furnace 60 is heated by a heating device 61 .
  • the internal temperature of the CNT synthesis furnace 60 during heating is preferably 800° C. or higher and 1500° C. or lower, more preferably 900° C. or higher and 1400° C. or lower, and even more preferably 1000° C. or higher and 1200° C. or lower.
  • the heated carbon-containing gas may be supplied from the carbon-containing gas supply port 62 to the CNT synthesis furnace 60 , or the carbon-containing gas may be heated in the CNT synthesis furnace 60 .
  • the diameter ( ⁇ ) of the cross section of the carbon nanotube synthesis furnace 60 is preferably ⁇ 30 mm or more, more preferably ⁇ 100 mm or more, and even more preferably ⁇ 300 mm or more, from the viewpoint of ensuring a sufficient amount of carbon nanotubes to be synthesized.
  • the upper limit of the cross-sectional area of the carbon nanotube synthesis furnace 60 is not particularly limited, it can be ⁇ 1 m or less from the viewpoint of device design.
  • the cross-sectional area of the carbon nanotube synthesis furnace 60 is preferably ⁇ 30 mm or more and ⁇ 1 m or less, more preferably ⁇ 50 mm or more and ⁇ 500 mm or less, and still more preferably ⁇ 100 mm or more and ⁇ 200 mm or less.
  • the cross-sectional diameter of the CNT synthesis furnace 60 means the diameter of the circular hollow portion of the CNT synthesis furnace in the cross section normal to the longitudinal direction (center line) of the CNT synthesis furnace.
  • the carbon-containing gas supply port 62 is provided at one end (the left end in FIG. 2) of the carbon nanotube synthesis furnace 60, and the carbon-containing gas is supplied from the carbon-containing gas supply port 62 to the CNT synthesis furnace 60. be.
  • a catalyst (not shown) is placed near the carbon-containing gas supply port in the CNT synthesis furnace 60 .
  • the carbon-containing gas supply port 62 can be configured to have a gas cylinder (not shown) and a flow control valve (not shown).
  • the first flow path 41 and the second flow path 42 are provided at the end of the carbon nanotube synthesis furnace 60 opposite to the end where the carbon-containing gas supply port 62 is provided.
  • the first channel 41 is provided in the first A structure 40A.
  • the second channel 42 is provided in the first B structure 40B.
  • the first A structure 40A includes a tubular first A-1 part 40A-1 and a funnel connected to the end of the first A-1 part 40A-1 on the carbon-containing gas supply port 62 side (left side in FIG. 2) It consists of a shaped first A-2 part 40A-2.
  • the small diameter end of the 1A-2 part 40A-2 is connected to the end of the 1A-1 part 40A-1. Therefore, in the 1A structure 40A, the large-diameter end of the 1A-2 part 40A-2 faces the carbon-containing gas supply port 62.
  • At least part of the first A structure 40A is preferably arranged inside the CNT synthesis furnace 60 . With the above configuration, the CNTs are easily taken into the first channel 41 .
  • the 1B structure 40B includes a tubular 1B-1 part 40B-1 and a funnel connected to the end of the 1B-1 part 40B-1 on the carbon-containing gas supply port 62 side (left side in FIG. 2) It consists of a shaped first B-2 part 40B-2.
  • the small diameter end of the 1B-2 part 40B-2 is connected to the end of the 1B-1 part 40B-1. Therefore, in the 1B structure 40B, the large-diameter end of the 1B-2 part 40B-2 faces the carbon-containing gas supply port 62.
  • At least part of the 1B structure 40B is preferably arranged inside the CNT synthesis furnace 60 . With the above configuration, CNTs are easily taken into the second flow path 42 .
  • the first channel 41 and the second channel 42 are provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace 60, and the cross-sectional area of each of the first channel 41 and the second channel 42 is equal to the carbon nanotube synthesis smaller than the cross-sectional area of the furnace 60; With the above configuration, a plurality of CNTs are aligned and aggregated along the longitudinal direction inside each of the first channel 41 and the second channel 42 to form a CNT assembly line.
  • the angle between the longitudinal direction (center line) of the CNT synthesis furnace 60 and the longitudinal direction (center line) of the first flow path 41 is 0° or more and 20° or less
  • the longitudinal direction of the CNT synthesis furnace 60 ( center line) and the longitudinal direction (center line) of the second flow path 42 is 0° or more and 20° or less.
  • the angle between the longitudinal direction (center line) of the first channel 41 and the longitudinal direction (center line) of the second channel 42 is 0° or more and 40° or less.
  • the cross-sectional area of the first flow channel 41 means the area of the first flow channel in the cross section normal to the longitudinal direction (center line) of the first flow channel, and the hollow portion of the first A structure equivalent to the cross-sectional area of As shown in FIG. 2, the first flow path consists of a hollow portion of a 1A structure 40A consisting of a tubular 1A-1 part 40A-1 and a funnel-shaped 1A-2 part 40A-2,
  • the cross-sectional area of the hollow portion is not constant, "the cross-sectional area of the first channel is smaller than the cross-sectional area of the CNT synthesis furnace.” is smaller than the cross-sectional area of the hollow part of the CNT synthesis furnace.
  • the largest cross-sectional area among the cross-sectional areas of the first channel corresponds to the cross-sectional area at the end of the first A-2 part 40A-2 closest to the carbon-containing gas supply port 62 .
  • the relationship between the cross-sectional area of the second channel 42 and the cross-sectional area of the CNT synthesis furnace 60 is defined similarly to the relationship between the cross-sectional area of the first channel 41 and the cross-sectional area of the CNT synthesis furnace 60 described above.
  • each of the first channel 41 and the second channel 42 is smaller than the cross-sectional area of the carbon nanotube synthesis furnace 60 . According to this, a tensile force in the direction toward the downstream side of the carbon-containing gas can be applied to the CNTs in the first channel and the second channel. When a tensile force acts on the ends of the carbon nanotubes, the carbon nanotubes extending from the catalyst particles 27 are pulled and elongated in the longitudinal direction while being plastically deformed and reduced in diameter. Therefore, it is easy to orient and lengthen the CNT-assembled wire.
  • the cross-sectional area of each of the first channel 41 and the second channel 42 can be appropriately set according to the desired diameter of the CNT-aggregated wire.
  • the lower limit of the cross-sectional area of each of the first flow channel 41 and the second flow channel 42 is preferably 0.1 mm 2 or more, more preferably 1 mm 2 or more, from the viewpoint that the diameter of the CNT aggregate line can be easily made ⁇ 10 ⁇ m or more, and 10 mm 2 or more is more preferable.
  • the upper limit of the cross-sectional area of each of the first channel 41 and the second channel is preferably 300 mm 2 or less, more preferably 200 mm 2 or less, and even more preferably 100 mm 2 or less.
  • two channels, the first channel and the second channel are provided in parallel on the end side of the CNT synthesis furnace. It can be as above.
  • the number of channels provided in parallel corresponds to the number of CNT-assembled wires to be manufactured. Therefore, by increasing the number of flow paths provided in parallel, it is possible to increase the number of CNT assembly wires manufactured using one CNT synthesis furnace.
  • the cross-sectional area of the CNT synthesis furnace 60 is not particularly limited as long as it is a size that allows the first channel 41 and the second channel 42 to be provided inside the CNT synthesis furnace.
  • the lower limit of the cross-sectional area of the CNT synthesis furnace is preferably, for example, 500 mm 2 or more, more preferably 5000 mm 2 or more, and even more preferably 50000 mm 2 or more, from the viewpoint of improving the production efficiency of the CNT wire assembly.
  • the upper limit of the cross-sectional area of the CNT synthesis furnace is not particularly limited, it can be, for example, 1 m 2 or less from the viewpoint of production equipment.
  • the cross-sectional area of the CNT synthesis furnace is preferably 500 mm 2 or more and 1 m 2 or less, more preferably 5000 mm 2 or more and 50000 mm 2 or less, and even more preferably 10000 mm 2 or more and 20000 mm 2 or less.
  • the first A structure and the first B structure preferably have the same shape. According to this, the shape of the CNT assembly lines collected from each structure becomes substantially uniform.
  • the CNT-assembled wire manufacturing apparatus of the present embodiment preferably includes a liquid deposition device 63 that deposits a volatile liquid on the carbon nanotube-assembled wires 31 and 32 .
  • the details of the volatile liquid are described in Embodiment 1, so the description thereof will not be repeated.
  • the liquid deposition device 63 is arranged at a position where the volatile liquid can be deposited on the carbon nanotube assembly lines 31 and 32 .
  • the liquid deposition device 63 can be arranged downstream of the carbon-containing gas from the first channel 41 and the second channel 42 .
  • the CNT-assembled wire manufacturing apparatus of the present embodiment preferably includes a winding device 64 that winds the carbon nanotube-assembled wires 31 and 32 while applying tension to the carbon nanotube-assembled wires 31 and 32 . It is possible to obtain a CNT stranded wire having high strength by applying tension to the CNT stranded wire and winding it while stretching it.
  • FIG. 3 is a diagram showing a flow chart of a method for manufacturing a carbon nanotube stranded wire according to this embodiment.
  • FIG. 4 is a diagram showing an example of a carbon nanotube stranded wire manufacturing apparatus used in the carbon nanotube stranded wire manufacturing method of the present embodiment.
  • FIG. 5 is a diagram showing the main surface of the 1-1 structure provided in the CNT assembly line manufacturing apparatus of FIG. 4 on the carbon-containing gas supply port 62 side. 6 is a cross-sectional view along the longitudinal direction of the CNT synthesis furnace of the first and second flow paths provided in the CNT assembly line manufacturing apparatus of FIG. 4.
  • FIG. 3 is a diagram showing a flow chart of a method for manufacturing a carbon nanotube stranded wire according to this embodiment.
  • FIG. 4 is a diagram showing an example of a carbon nanotube stranded wire manufacturing apparatus used in the carbon nanotube stranded wire manufacturing method of the present embodiment.
  • FIG. 5 is a diagram showing the main surface of the 1-1
  • the method for producing a CNT-assembled wire of the present embodiment is similar to the method for producing a CNT-assembled wire of the first embodiment,
  • the first carbon nanotube group 11 includes a first A carbon nanotube group 11A composed of a portion of the plurality of carbon nanotubes constituting the first carbon nanotube group 11, and a plurality of carbon nanotube groups 11A constituting the first A carbon nanotube group 11A.
  • the first flow path includes a 1-1A flow path 41A and a 1-1a flow path 41a provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace, and the 1-1A flow path 41A and the 1-1A flow path 41A.
  • the 2A step is a 2A-1A step of orienting and assembling the 1A carbon nanotube groups 11A along the longitudinal direction of the carbon nanotubes in the 1-1A channel 41A to obtain a 1A carbon nanotube-assembled wire 21A; a 2A-1a step of orienting and assembling the 1a carbon nanotube groups 11a along the longitudinal direction of the carbon nanotubes in the 1a channel 41a to obtain a 1a carbon nanotube assembly strand 21a; A plurality of carbon nanotube-assembled strands including the 1A carbon nanotube-assembled strand 21A and the 1a carbon nanotube-assembled strand 21a are arranged in the first-second channel 41C along the longitudinal direction of the carbon nanotube-assembled strand.
  • the second carbon nanotube group 12 includes a second B carbon nanotube group 12B composed of a part of the plurality of carbon nanotubes constituting the second carbon nanotube group, and a plurality of carbon nanotubes constituting the second B carbon nanotube group 12B.
  • a second carbon nanotube group 12b composed of a part of the plurality of carbon nanotubes constituting the second carbon nanotube group 12 different from nanotubes
  • the second flow path includes a 2-1B flow path 42B and a 2-1b flow path 42b provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace, and the 2-1B flow path 42B and the 2-1B flow path 42B.
  • the 2B step above is a 2B-1B step of orienting and assembling the 2B carbon nanotube groups 12B along the longitudinal direction of the carbon nanotubes in the 2-1B channel 42B to obtain a 2B carbon nanotube-aggregated strand 22B; a 2B-1b step of orienting and assembling the 2b carbon nanotube groups 12b along the longitudinal direction of the carbon nanotubes in the 2b channel 42b to obtain a 2b carbon nanotube aggregated wire 22b; A plurality of carbon nanotube-assembled strands including the 2B carbon nanotube-assembled strand 22B and the 2b carbon nanotube-assembled strand 22b are arranged along the longitudinal direction of the carbon nanotube-assembled strand within the 2-2 channel 42D.
  • the plurality of carbon nanotubes constituting the first carbon nanotube group 11 are in a separated state before entering the first channel 41 without forming a network that hinders the separation. It is preferable that the plurality of carbon nanotubes constituting the second carbon nanotube group 12 are in a state of being separated from each other before entering the second channel 42 without forming a network that hinders the separation. According to this, it is possible to prevent clogging of the plurality of carbon nanotubes near the entrance of the first channel and near the entrance of the second channel.
  • the 1-1A channel, the 1-1a channel, the 2-1B channel and the 2-1b channel are also referred to as "upstream channel”.
  • the 1-2 channel and the 2-2 channel are also referred to as "downstream channel”.
  • two CNT-assembled wires can be produced using one CNT synthesis furnace.
  • the second step includes two steps, 2A step and 2B step, and shows the case of obtaining two CNT-assembled lines, but the form of the second step is not limited to this. .
  • the channels the number of channels (downstream channels, corresponding to the first-second channel 41C and the second-second channel 42D in FIG. 4) arranged on the downstream side of the carbon-containing gas is arranged in parallel. By increasing it, the number of CNT-assembled wires obtained can be increased.
  • the number of downstream channels matches the number of CNT assembly lines obtained. Therefore, if the number of downstream flow paths is three, three CNT assembly lines are obtained, and if the number of downstream flow paths is four, four CNT assembly lines are obtained.
  • the method for manufacturing a carbon nanotube-assembled wire according to this embodiment basically includes all the steps of the method for manufacturing a CNT-assembled wire according to the first embodiment.
  • the difference from the CNT-assembled wire manufacturing method of Embodiment 1 is that each of the 2A step and the 2B step is a step of obtaining a plurality of carbon nanotube-assembled wires (hereinafter also referred to as "CNT-assembled wires").
  • 2A-1A step, 2A-1a step, 2B-1B step, 2B-1b step) and aligning and assembling a plurality of CNT-aggregated wires along their longitudinal direction to obtain a CNT-aggregated wire (Step 2A-2, Step 2B-2). Therefore, 2A-1A step, 2A-1a step, 2A-2 step, 2B-1B step, 2B-1b step, and 2B-2 step will be described below.
  • the 2A-1A step, the 2A-1a step, the 2B-1B step, and the 2B-1b step each form a carbon nanotube group consisting of a plurality of carbon nanotubes in the upstream channel along the longitudinal direction of the carbon nanotubes.
  • the carbon nanotubes are oriented and assembled to obtain a carbon nanotube-assembled wire.
  • the 2A-1 step will be described below.
  • the 1A carbon nanotube group 11A composed of a plurality of CNTs synthesized in the CNT synthesis furnace 60 is arranged in the 1-1A flow with the longitudinal direction of the CNTs along the flow of the carbon-containing gas. Intrude into the path 41A.
  • the 1-1A channel 41A is arranged such that its longitudinal direction follows the flow of the carbon-containing gas.
  • the cross-sectional area normal to the carbon-containing gas flow of the 1-1A channel 41A is smaller than the cross-sectional area normal to the carbon-containing gas flow of the CNT synthesis furnace 60 . Therefore, the plurality of CNTs that have entered the 1-1A channel 41A are oriented and aggregated along the longitudinal direction of the CNTs in the 1-1A channel 41A to form the 1A carbon nanotube aggregate strand 21A. to form
  • the lower limit of the number of carbon nanotubes constituting the 1A carbon nanotube group is preferably 1,000 or more, more preferably 1,000,000 or more, and still more preferably 100,000,000 or more, from the viewpoint of lengthening the carbon nanotube aggregate strand.
  • the upper limit of the number of carbon nanotubes constituting the 1A carbon nanotube group is preferably 1 trillion or less, more preferably 10 billion or less, and even more preferably 1 billion or less, from the viewpoint of preventing clogging of the channel.
  • the number of carbon nanotubes constituting the 1A carbon nanotube group is preferably 10,000 to 1,000,000,000, more preferably 100,000 to 100,000,000, and still more preferably 1,000,000 to 100,000,000.
  • the number of Karnon nanotubes forming the 1A carbon nanotube group means the number of carbon nanotubes simultaneously passing through the opening of the 1-1A channel 41A on the carbon-containing gas supply port side.
  • the shape of the 1A carbon nanotube aggregated wire 21A obtained by the 2A-1A step is a thread shape in which a plurality of carbon nanotubes are aligned and aggregated in their longitudinal direction.
  • the length of the carbon nanotube-assembled wire (hereinafter also referred to as "CNT-assembled wire") is not particularly limited as long as it can form the carbon nanotube-assembled wire in the next step 2A-2.
  • the size of the diameter of the carbon nanotube aggregate strand is not particularly limited, and can be appropriately adjusted depending on the application.
  • the lower limit of the diameter of the CNT aggregate wire is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more.
  • the upper limit of the diameter of the CNT aggregate wire is not particularly limited, it can be 100 ⁇ m or less from the viewpoint of manufacturing.
  • the diameter of the CNT aggregate wire is preferably 0.1 ⁇ m or more and 100 ⁇ m or less, more preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the diameter of the CNT wire assembly is smaller than the length of the CNT wire assembly. That is, the lengthwise direction of the CNT aggregate wire corresponds to the longitudinal direction.
  • the diameter of a carbon nanotube-assembled strand means the average outer diameter of one CNT-assembled strand.
  • the average outer diameter of one CNT-aggregated wire is obtained by observing a cross section at any two points of one CNT-aggregated wire with a transmission electron microscope or a scanning electron microscope. It is obtained by measuring the outer diameter, which is the distance between the two most distant points, and calculating the average value of the obtained outer diameters.
  • the fact that the plurality of CNTs are aligned and aggregated in the longitudinal direction is the same as that described in Embodiment 1, “In the CNT-assembled wire, the plurality of CNTs are aligned in these It can be confirmed by the same method as the method for confirming that the particles are oriented and aggregated in the longitudinal direction. Therefore, the description thereof will not be repeated.
  • the degree of orientation of CNTs in the carbon nanotube aggregate strand is preferably 0.8 or more and 1.0 or less.
  • the CNT-aggregated wire is elongated while maintaining the electrical conductivity and mechanical strength of the CNT.
  • the 2A-1a step, the 2B-1B step and the 2B-1b step are basically the same steps as the 2A-1 step and will not be described repeatedly.
  • ⁇ 2A-2 step, 2B-2 step> In the 2A-2 step and the 2B-2 step, respectively, a plurality of CNT-assembled wires are aligned and assembled along the longitudinal direction of the carbon nanotube-assembled wires in the downstream channel to form a carbon nanotube-assembled wire. It is a process of obtaining As a representative of these steps, the 2A-2 step will be described below.
  • a plurality of carbon nanotube aggregated elements including the 1A carbon nanotube aggregated strands 21A obtained in the step 2A-1A and the first carbon nanotube aggregated strands 21a obtained in the step 2A-1a.
  • the wire enters the 1-2 channel 41C with the longitudinal direction of the CNT-aggregated wire along the flow of the carbon-containing gas.
  • the first-second flow path 41C is arranged such that its longitudinal direction follows the flow of the carbon-containing gas.
  • the plurality of CNT-assembled wires that have entered the 1-2 channel 41C are oriented and aggregated along the longitudinal direction of the CNT-assembled wires in the 1-2 channel 41C to form first carbon nanotubes.
  • a collective line 31 is formed.
  • the plurality of carbon nanotube aggregated strands coming out of the upstream flow path (1-1A flow path, 1-1a flow path) are separated from each other.
  • the carbon nanotubes are not entangled in the oriented state, and can be oriented and aggregated in the longitudinal direction in the downstream channel to form an aggregated line of carbon nanotubes.
  • the lower limit of the number of carbon nanotube-assembled wires constituting the first carbon nanotube-assembled wire is preferably 2 or more, more preferably 10 or more, and further preferably 100 or more, from the viewpoint of lengthening the carbon nanotube-assembled wire.
  • the upper limit of the number of carbon nanotube stranded wires constituting the first carbon nanotube stranded wire is preferably 10,000 or less, more preferably 1,000 or less, and even more preferably 300 or less, from the viewpoint of preventing clogging of the flow path.
  • the number of carbon nanotube aggregated wires constituting the first carbon nanotube aggregated wire is preferably 2 or more and 10000 or less, more preferably 10 or more and 1000 or less, and still more preferably 100 or more and 300 or less.
  • the number of carbon nanotube-assembled wires constituting the first carbon nanotube-assembled wire is the number of carbon nanotube-assembled wires simultaneously passing through the opening on the carbon-containing gas supply port side of the 1-2 channel 41C.
  • the shape of the carbon nanotube assembly wire is a string shape in which a plurality of carbon nanotube assembly wires are aligned and assembled in their longitudinal direction. It can be confirmed by observation with an optical microscope or a scanning electron microscope that the CNT-assembled wire has a string shape in which a plurality of carbon nanotube-assembled wires are aligned in their longitudinal direction.
  • the length of the carbon nanotube aggregated wire obtained in this embodiment is not particularly limited, and can be appropriately adjusted depending on the application.
  • the lower limit of the length of the CNT-assembled wire is, for example, preferably 100 ⁇ m or longer, more preferably 1000 ⁇ m or longer, and even more preferably 10 cm or longer.
  • the upper limit of the length of the CNT-assembled wire is not particularly limited, it is preferably 100 km or less from the viewpoint of manufacturing.
  • the length of the CNT aggregate line is preferably 100 ⁇ m or more and 10 km or less, more preferably 1000 ⁇ m or more and 1 km or less, and even more preferably 10 cm or more and 100 m or less.
  • the length of the CNT-assembled line can be measured by observation with an optical microscope or by visual inspection.
  • the size of the diameter of the carbon nanotube aggregated wire obtained in this embodiment is not particularly limited, and can be appropriately adjusted depending on the application.
  • the diameter of the CNT-assembled wire is, for example, preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the upper limit of the diameter of the CNT-assembled wire is not particularly limited, it is preferably 10000 ⁇ m or less from the viewpoint of production. In this embodiment, the diameter of the CNT-assembled wire is smaller than the length of the CNT-assembled wire.
  • the degree of orientation of the CNT-aggregated wires in the carbon nanotube-aggregated wire is basically a value calculated in the same procedure as (a1) to (a6) described in the method for calculating the orientation degree of Embodiment 1. is. The difference is that in the procedure of (a1), the following equipment is used to image the CNT aggregate line under the following conditions.
  • the carbon nanotube aggregated wire in the carbon nanotube aggregated wire are oriented in its longitudinal direction and aggregated.
  • the carbon nanotubes are oriented with an orientation degree of 0.9 or more and 1 or less in the carbon nanotube aggregated wire, and the carbon nanotube aggregated wire has a carbon nanotube aggregated wire of 0.8 or more. Orientation with a degree of orientation of 1 or less is preferred. This means that in the CNT-assembled wire of the present embodiment, the orientation of the CNTs and the CNT-assembled wire is high. According to this, the CNT-assembled wire can have excellent electrical conductivity and mechanical strength.
  • a carbon nanotube-assembled wire manufacturing apparatus 100b of the present embodiment basically has all the configurations of the carbon nanotube-assembled wire manufacturing apparatus of the second embodiment. 4 and 6, the first flow path is provided in parallel on the side of the carbon-containing gas supply port 62 of the carbon nanotube synthesis furnace 60.
  • the 1-1A channel 41A and the 1-1a channel 41a, and the 1-2 channel provided on the opposite side of the carbon-containing gas supply port 62 of the 1-1A channel 41A and the 1-1a channel 41a 2-1B flow path 42B and 2-1b flow path 42b provided in parallel on the carbon-containing gas supply port side of the carbon nanotube synthesis furnace 60; 2-1B channel 42B and 2-2 channel 42D provided on the opposite side of carbon-containing gas supply port 62 of 2-1B channel 42b.
  • Differences from the CNT-assembled wire manufacturing apparatus of the second embodiment will be described below.
  • the 1-1A channel 41A, the 1-1a channel 41a, the 2-1B channel 42B and the 2-1b channel 42b are the same first
  • the 1-2 flow path 41C is provided in the 1-2 structure 52A different from the 1-1 structure 51
  • the 2-2 flow path 42D is provided in the 1-1 structure 51. It is provided in the 2-2 structure 52B different from the -1 structure 51 .
  • the 1-1 structure 51 is a porous body having a large number of thin cylindrical through holes. Each through hole corresponds to each channel.
  • the 1-1 structure 51 has through holes corresponding to the 1-1A channel 41A, the 1-1a channel 41a, the 2-1B channel 42B, and the 2-1b channel 42b.
  • the cross-sectional shape of each through-hole is preferably a regular hexagon from the viewpoint of suppressing the deposition of CNTs in the through-hole and ensuring the strength of the 1-1 structure.
  • the cross-sectional area of each through-hole can be appropriately changed according to the desired diameter and length of the CNT-aggregated wire.
  • the lower limit of the cross-sectional area of each through-hole is preferably 0.005 mm 2 or more, preferably 0.01 mm 2 or more, preferably 0.05 mm 2 or more, and 0.1 mm 2 or more. More preferably, it is 0.5 mm 2 or more.
  • the upper limit of the cross-sectional area of each through-hole is preferably, for example, 100 mm 2 or less, more preferably 50 mm 2 or less, and even more preferably 10 mm 2 or less, from the viewpoint of ease of CNT aggregation.
  • the cross-sectional area of each through-hole means the area of the cross-section normal to the longitudinal direction of the hollow portion surrounded by the 1-1 structure forming the outer edge of the through-hole.
  • the cross-sectional area of each through-hole is preferably constant from the upstream side to the downstream side.
  • the constant cross-sectional area means that the maximum and minimum values of the cross-sectional area are within ⁇ 5% of the average value.
  • the lower limit of the length of the through-hole in the longitudinal direction is preferably 5 mm or more, more preferably 10 mm or more, and even more preferably 30 mm or more, from the viewpoint of sufficiently assembling the CNTs.
  • the upper limit of the length of the through-hole in the longitudinal direction is preferably 1000 mm or less, more preferably 300 mm or less, and 100 mm or less from the viewpoint of suppressing the deposition of CNTs on the inner wall of the through-hole and increasing the amount of collected CNT-aggregated wires. is more preferred.
  • the length of the through hole in the longitudinal direction is preferably 5 mm or more and 1000 mm or less, more preferably 10 mm or more and 300 mm or less, and even more preferably 30 mm or more and 100 mm or less.
  • the number of through-holes provided in the 1-1 structure can be appropriately set in consideration of the cross-sectional area of the hollow part of the CNT synthesis furnace, the cross-sectional area of each through-hole, the desired number of CNT aggregate strands, etc. can.
  • the lower limit of the number of through-holes provided in the 1-1 structure is preferably 1/10 cm 2 or more, more preferably 1/cm 2 or more, and 1/mm 2 from the viewpoint of improving manufacturing efficiency. The above is more preferable.
  • the upper limit of the number of through-holes provided in the 1-1 structure is not particularly limited, and can be, for example, 100/mm 2 or less.
  • the number of through-holes provided in the 1-1 structure is preferably 1/10 cm 2 or more and 100/mm 2 or less, more preferably 1/cm 2 or more and 100/mm 2 or less, and 1/mm 2 or more and 10 pieces/mm 2 or less is more preferable.
  • the cross-sectional area of the 1-1 structure is not limited, and can be set according to the cross-sectional area of the hollow portion of the CNT synthesis furnace.
  • the cross-sectional area of the 1-1 structure means the area of the region surrounded by the outer edge of the 1-1 structure, including the through holes.
  • the lower limit of the cross-sectional area of the 1-1 structure is preferably 100 mm 2 or more, more preferably 1000 mm 2 or more, and even more preferably 10000 mm 2 or more, from the viewpoint of improving the production efficiency of the CNT-assembled wire.
  • the upper limit of the cross-sectional area of the 1-1 structure is not particularly limited, it can be, for example, 1 m 2 or less from the viewpoint of manufacturing equipment.
  • the cross-sectional area of the 1-1 structure is preferably 100 mm 2 or more and 1 m 2 or less, more preferably 1000 mm 2 or more and 0.3 m 2 or less, and still more preferably 10000 mm 2 or more and 0.1 m 2 or less.
  • the 1-1 structure is ceramics (alumina, zirconia, aluminum nitride, silicon carbide, silicon nitride, forsterite, steatite, cordierite, mullite, ferrite, gadolinium oxide, etc.), quartz glass, glass, metals, graphite can consist of Among them, it is preferable to use ceramics from the viewpoint of heat resistance and durability required in CNT production. Furthermore, it is preferable to form arbitrary flow paths by 3D printer technology.
  • 1-2 structure 52A and the 2-2 structure 52B can basically have the same configurations as the 1A structure and the 1B structure of Embodiment 2, the description thereof will not be repeated. .
  • FIG. 7 is a diagram showing an example of a carbon nanotube stranded wire manufacturing apparatus used in the carbon nanotube stranded wire manufacturing method of the present embodiment.
  • FIG. 8 is a view showing the main surface of the 1-3 structure 53 provided in the CNT assembly wire manufacturing apparatus of FIG. 7 on the carbon-containing gas supply port 62 side.
  • FIG. 9 is a diagram showing the main surface opposite to the main surface on the carbon-containing gas supply port 62 side of the 1-3 structure 53 provided in the CNT assembly wire manufacturing apparatus of FIG.
  • FIG. 10 is a cross-sectional view along the longitudinal direction of the CNT synthesis furnace of the 1-3 structure 53 provided in the CNT assembly wire manufacturing apparatus of FIG. Differences from the CNT-assembled wire manufacturing apparatus of the fourth embodiment will be described below.
  • the channel 42b and the 2-2 channel 42D are provided in the same 1-3 structure 53, and are connected to the carbon-containing gas supply ports 62 of the 1-1A channel 41A and the 1-1a channel 41a, respectively.
  • the opposite end is connected to the end of the carbon-containing gas supply port 62 side of the 1-2 channel 41C, and the carbon-containing gas of each of the 2-1B channel 42B and the 2-1b channel 42b
  • the end opposite to the supply port 62 is connected to the end of the 2-2 channel 42D on the carbon-containing gas supply port 62 side.
  • the 1-3 structure 53 is a porous body having a large number of narrow cylindrical through holes.
  • the through holes correspond to flow channels.
  • a plurality of openings (hereinafter also referred to as "first openings") are provided, including an opening forming the end of 42b.
  • openings forming the ends of the 1-2 channel 41C and the 2-2 channel 42D are formed.
  • a plurality of openings (hereinafter also referred to as "second openings”) are provided.
  • a plurality of CNTs that have entered the 1-1A channel 41A and the 1-1a channel 41a are oriented in the longitudinal direction and aggregated to form CNT aggregate strands 21A and 21a.
  • a plurality of CNT-assembled wires including the CNT-assembled wires 21A and 21a are aligned in the longitudinal direction and gathered to form a CNT-assembled wire 31. As shown in FIG.
  • a plurality of CNTs that have entered the 2-1B channel 42B and the 2-1b channel 42b are oriented in the longitudinal direction and aggregated to form CNT aggregate strands 21B and 21b.
  • a plurality of CNT-assembled wires including the CNT-assembled wires 21B and 21b are aligned in the longitudinal direction and aggregated to form the CNT-assembled wire 32. As shown in FIG.
  • the formation of the CNT-aggregated wire and the CNT-aggregated wire is continuously performed inside the 1-3 structure 53 . This improves the production efficiency of the CNT aggregated wire.
  • the number of channels connected to the 1-2 channel 41C is not limited to two, the 1-1A channel 41A and the 1-1a channel 41a. It can be set as appropriate.
  • the lower limit of the number of channels connected to the first-second channel 41C is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more, from the viewpoint of preventing turbulence due to turbulent flow or the like.
  • the upper limit of the number of channels connected to the 1-2 channel 41C is not particularly limited, but it can be 100 or less from the viewpoint of manufacturing the 1-3 structure.
  • the number of channels connected to the first-second channel 41C is preferably 2 or more and 100 or less, more preferably 5 or more and 50 or less, and even more preferably 10 or more and 20 or less.
  • the number of channels connected to the 2nd-2nd channel 42D can also be set in the same manner as the number of channels connected to the 1st-2nd channel 41C.
  • the lower limit of the cross-sectional area of the through-holes forming the 1-1A channel 41A, the 1-1a channel 41a, the 2-1B channel 42B, and the 2-1b channel 42b prevents CNT clogging. From a viewpoint, it is preferably 0.005 mm 2 or more, preferably 0.01 mm 2 or more, preferably 0.05 mm 2 or more, more preferably 0.1 mm 2 or more, and still more preferably 0.5 mm 2 or more.
  • the upper limit of the cross-sectional area of each through-hole is preferably, for example, 100 mm 2 or less, more preferably 50 mm 2 or less, and even more preferably 10 mm 2 or less, from the viewpoint of ease of CNT aggregation.
  • the cross-sectional area of each through-hole means the area of the region surrounded by the 1-3 structure forming the outer edge of the through-hole.
  • the cross-sectional area of each through-hole is preferably constant from the upstream side to the downstream side.
  • the constant cross-sectional area means that the maximum and minimum values of the cross-sectional area are within ⁇ 5% of the average value.
  • the lower limit of the length is preferably 10 mm or longer, more preferably 20 mm or longer, and even more preferably 50 mm or longer, from the viewpoint of sufficient aggregation of CNTs.
  • the upper limit of the length of the through-hole in the longitudinal direction is preferably 1000 mm or less, more preferably 500 mm or less, and 100 mm or less from the viewpoint of suppressing the deposition of CNTs on the inner wall of the through-hole and increasing the amount of collected CNT-aggregated strands. is more preferred.
  • the length of the through hole in the longitudinal direction is preferably 10 mm or more and 1000 mm or less, more preferably 20 mm or more and 500 mm or less, and even more preferably 30 mm or more and 1000 mm or less.
  • the lower limit of the cross-sectional area of the through-holes forming the 1-2 flow path 41C and the 2-2 flow path 42D is preferably 0.01 mm 2 or more, and 0.01 mm 2 or more.
  • 02 mm 2 or more is preferable, 0.1 mm 2 or more is preferable, 0.2 mm 2 or more is more preferable, and 0.5 mm 2 or more is still more preferable.
  • the upper limit of the cross-sectional area of each through-hole is preferably, for example, 100 mm 2 or less, more preferably 10 mm 2 or less, and even more preferably 1 mm 2 or less, from the viewpoint of ease of assembly of the CNT wire assembly.
  • the lower limit of the length of the through-holes forming the 1-2 channel 41C and the 2-2 channel 42D in the longitudinal direction is said to sufficiently assemble the CNT-aggregated strands. From the viewpoint, it is preferably 5 mm or more, more preferably 10 mm or more, and even more preferably 20 mm or more.
  • the upper limit of the length of the through-hole in the longitudinal direction is preferably 1000 mm or less, more preferably 100 mm or less, from the viewpoint of suppressing deposition of the CNT wire assembly on the inner wall of the through-hole and increasing the collection amount of the CNT wire assembly. 50 mm or less is more preferable.
  • the length of the through hole in the longitudinal direction is preferably 5 mm or more and 1000 mm or less, more preferably 10 mm or more and 100 mm or less, and even more preferably 5 mm or more and 50 mm or less.
  • the CNT wire assembly manufacturing apparatus of this embodiment can include a CNT wire assembly guide tube 65 provided on the opposite side of the carbon-containing gas supply port 62 of the 1-3 structure 53 . It is preferable that the CNT assembly wire guide pipe is provided on the downstream extension of each of the 1-2 channel 41C and the 2-2 channel 42D provided in the 1-3 structure. As a result, the plurality of CNT assembly lines coming out of the 1-3 structure 53 are recovered in a separated state without being entangled with each other.
  • Example 1 As the apparatus 1, a carbon nanotube stranded wire manufacturing apparatus having the same configuration as the carbon nanotube stranded wire manufacturing apparatus shown in FIG. 2 is prepared. A specific configuration is as follows.
  • the apparatus 1 is provided at one end of the carbon nanotube synthesis furnace (quartz tube, hollow diameter 50 mm (cross-sectional area: approximately 2000 mm 2 ), length 50 mm) (left side in FIG. 2). and a first channel (maximum diameter 10 mm, 500 mm in length) and a second flow path (maximum diameter of 10 mm, length of 500 mm).
  • the first flow path and the second flow path are provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace.
  • the distance from the end of the CNT synthesis furnace on the carbon-containing gas supply port side to the carbon-containing gas supply port-side ends of the first channel and the second channel is 2000 mm.
  • a slurry sprayer in which a catalyst (ferrocene) is dissolved in toluene is placed near the carbon-containing gas supply port inside the CNT synthesis furnace.
  • a CNT assembly wire winding device is arranged downstream of the first flow path and the second flow path.
  • a carbon nanotube assembly wire of the sample 1 is produced.
  • apparatus 1 while supplying argon gas with an argon gas concentration of 100% by volume from the carbon-containing gas supply port into the CNT synthesis furnace at a flow rate of 1000 cc / min (flow rate of 3.4 cm / sec) for 50 minutes, The temperature is raised to 1200°C.
  • argon gas is switched to hydrogen gas (1000 cc/min), methane gas at a flow rate of 50 cc/min (flow rate 0.17 cm/sec), and carbon disulfide (CS 2 ) gas at a flow rate of 1 cc/min ( 120 minutes at a flow rate of 0.003 cm/sec).
  • the flow velocity of the entire mixed gas (carbon-containing gas) containing hydrogen gas, methane gas, and carbon disulfide is 3.6 cm/sec.
  • catalyst particles are released into the CNT synthesis furnace. After that, CNTs grow in the CNT synthesis furnace, and the CNTs aggregate inside the first channel and the second channel to form two CNT aggregate lines.
  • the CNT-assembled wire is wound by a winding device, and two CNT-assembled wires are recovered.
  • the orientation degrees of CNTs in the two CNTs of sample 1 are 0.8 and 0.9, respectively. This confirms that the CNTs are oriented and aggregated in the longitudinal direction in the CNT-aggregated line obtained by the apparatus 1 .
  • the lengths of the two CNTs of sample 1 are 10 m and 12 m, respectively.
  • the diameters of the two CNTs of sample 1 are ⁇ 0.1 mm and ⁇ 0.08 mm, respectively.
  • Example 2 As the apparatus 2, a carbon nanotube stranded wire manufacturing apparatus having the same configuration as the carbon nanotube stranded wire manufacturing apparatus shown in FIG. 4 is prepared. A specific configuration is as follows.
  • Apparatus 2 includes a carbon nanotube synthesis furnace (alumina tube, hollow diameter 80 mm (cross-sectional area 6000 mm 2 (cross-sectional shape: substantially circular)), length 2000 mm) and one end of the carbon nanotube synthesis furnace (Fig. 4 The carbon-containing gas supply port provided on the left side) and the end portion opposite to the end where the carbon-containing gas supply port of the carbon nanotube synthesis furnace is provided (right side in FIG. 4).
  • a carbon nanotube synthesis furnace alumina tube, hollow diameter 80 mm (cross-sectional area 6000 mm 2 (cross-sectional shape: substantially circular)), length 2000 mm
  • Fig. 4 The carbon-containing gas supply port provided on the left side) and the end portion opposite to the end where the carbon-containing gas supply port of the carbon nanotube synthesis furnace is provided (right side in FIG. 4).
  • 1 structure cross-sectional area of 1-1A channel, 1-1a channel, 2-1B channel and 2-1b channel 1 mm 2 , total number of channels (total through holes) 20 / inch , length 50 mm), and the 1-2 structure provided downstream of the 1-1 structure (1-2 flow path: maximum diameter 30 mm, length 1000 mm) and 2-2 structure ( 2-2 channel: maximum diameter 30 mm, length 1000 mm).
  • the distance from the end of the CNT synthesis furnace on the side of the carbon-containing gas supply port to the end of the structure 1-1 on the side of the carbon-containing gas supply port is 2500 mm.
  • a catalyst (ferrocene) is placed near the carbon-containing gas supply port inside the CNT synthesis furnace.
  • a CNT assembly wire winding device is arranged downstream of the 1-2 structure and the 2-2 structure. It is preferable that each of the channels 2-1, 2-2, etc. is sucked from the upstream side to the downstream side to efficiently gather the CNT aggregated wires coming out of the honeycomb and promote the assembly.
  • a carbon nanotube assemble wire of the sample 2 is produced.
  • apparatus 2 while supplying argon gas having an argon gas concentration of 100% by volume from the carbon-containing gas supply port into the CNT synthesis furnace at a flow rate of 1000 cc / min (flow rate of 3.4 cm / sec) for 50 minutes, The temperature is increased to 1000°C.
  • argon gas is switched to hydrogen gas (4000 cc/min), ethylene gas at a flow rate of 200 cc/min (flow rate 0.17 cm/sec), and carbon disulfide (CS 2 ) gas at a flow rate of 4 cc/min. (flow rate 0.003 cm/sec) for 120 minutes.
  • the flow velocity of the entire mixed gas (carbon-containing gas) containing argon gas, methane gas, and carbon disulfide is 3.6 cm/sec.
  • the catalyst collapses and catalyst particles are released into the CNT synthesis furnace.
  • CNTs grow in a CNT synthesis furnace, the CNTs are aggregated inside the 1-1 structure to form a CNT aggregate wire, and the CNT aggregate wire is the 1-2 structure and the 2-2nd structure.
  • Assembled inside each of the structures two CNT assembly lines are formed.
  • the CNT-assembled wire is wound by a winding device, and two CNT-assembled wires are recovered.
  • the orientation degrees of CNTs in the two CNT-assembled lines of sample 2 are 82 and 89, respectively.
  • the degrees of orientation of the CNT-assembled strands of the two CNT-assembled strands of Sample 2 are 86 and 92, respectively. This confirms that the CNTs and the CNT-aggregated wires are oriented and aggregated in the longitudinal direction in the CNT-aggregated wire obtained by the apparatus 2 .
  • the lengths of the two CNTs of sample 2 are 10 m and 15 m, respectively.
  • the respective diameters of the two CNTs of sample 2 are 0.8 mm and 1.2 mm.
  • Example 3 As the apparatus 3, a carbon nanotube-assembled wire manufacturing apparatus having the same configuration as the carbon nanotube-assembled wire manufacturing apparatus shown in FIG. 7 is prepared. A specific configuration is as follows.
  • Apparatus 3 includes a carbon nanotube synthesis furnace (alumina tube, hollow diameter ⁇ 50 mm, length 1500 mm) and a carbon-containing gas supply port provided at one end (left side in FIG. 7) of the carbon nanotube synthesis furnace.
  • the 1-3 structure (1-1A flow path, 1st -1a channel, 1-1B channel and 1-1b channel cross-sectional area 2 mm 2 , 1-2 channel and 2-2 channel cross-sectional area 2 mm 2 , 1-2 channel and 100 upstream through-holes, 50 mm long, 100 upstream main surface holes, and 2 downstream main surface holes connected to each of the 2-2 flow paths), and the first -1 Two guide tubes (diameter 5 mm, length 1000 mm) provided downstream of the structure.
  • the distance from the end of the CNT synthesis furnace on the side of the carbon-containing gas supply port to the end of the structure 1-3 on the side of the carbon-containing gas supply port is 2000 mm.
  • a catalyst (ferrocene) is placed near the carbon-containing gas supply port inside the CNT synthesis furnace.
  • a CNT wire winding device is arranged downstream of the guide tube.
  • a carbon nanotube assemble wire of the sample 3 is produced.
  • apparatus 3 while supplying argon gas with an argon gas concentration of 100% by volume from the carbon-containing gas supply port into the CNT synthesis furnace at a flow rate of 1000 cc / min (flow rate of 3.4 cm / sec) for 50 minutes, The temperature is raised to 1300°C.
  • argon gas is switched to hydrogen gas (1000 cc/min), methane gas at a flow rate of 50 cc/min (flow rate 0.17 cm/sec), and carbon disulfide (CS 2 ) gas at a flow rate of 1 cc/min ( 120 minutes at a flow rate of 0.003 cm/sec).
  • the flow velocity of the entire mixed gas (carbon-containing gas) containing argon gas, methane gas, and carbon disulfide is 3.6 cm/sec.
  • the catalyst collapses and catalyst particles are released into the CNT synthesis furnace. After that, CNTs grow in the CNT synthesis furnace, the CNTs aggregate inside the first to third structures to form two CNT aggregate lines, and the CNT aggregate lines enter the guide tube.
  • the CNT-assembled wire is wound by a winding device, and two CNT-assembled wires are recovered.
  • the orientation degrees of CNTs in the two CNT-assembled lines of Sample 3 are 0.86 and 0.93, respectively.
  • the degrees of orientation of the CNT-aggregated wires in the two CNT-aggregated wires of Sample 3 are 0.87 and 0.91, respectively. This confirms that the CNTs and the CNT-aggregated wires are oriented and aggregated in the longitudinal direction in the CNT-aggregated wire obtained by the apparatus 3 .
  • the lengths of the two CNT-assembled lines of sample 3 are 100 m and 150 m, respectively.
  • the respective diameters of the two CNTs of Sample 3 are 0.2 mm and 0.3 mm.
  • the device 4 As the device 4, a device having the configuration shown in FIG. 11 is prepared.
  • the device 4 basically has the same configuration as the device 1, except that the first channel, the second channel and the winding device are not provided.

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PCT/JP2022/007606 2021-02-25 2022-02-24 カーボンナノチューブ集合線の製造方法及びカーボンナノチューブ集合線製造装置 WO2022181692A1 (ja)

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